An investigation of the electrocatalysis of single-walled carbon nanotubes modified electrodes has been performed in this work. Nanotube-modified electrodes present a surface area much higher than the bare glassy carbon surfaces as determined by capacitance measurements. Several redox probes were selected for checking the reactivity of specific sites at the carbon nanotube surface. The presence of carbon nanotubes on the electrode improves the kinetics for all the reactions studied compared with the bare glassy carbon electrode with variations of the heterogeneous electron transfer rate constant up to 5 orders of magnitude. The most important effects are observed for the benzoquinone/hydroquinone and ferrocene/ferricinium redox couples, which show a remarkable improvement of their electron transfer kinetics on SWCNT-modified electrodes, probably due to strong π–π interaction between the organic molecules and the walls of the carbon nanotubes. For many of the reactions studied, less than 1% of the nanotube-modified electrode surface is transferring charge to species in solution. This result suggests that only nanotube tips are active sites for the electron transfer in such cases. On the contrary, the electroactive surface for the reactions of ferrocene and quinone is higher indicating that the electron transfer is produced also from the nanotube walls.